Seed crystal for growth of gallium nitride bulk crystal in supercritical ammonia and fabrication method.,/

ABSTRACT

In one instance, the seed crystal of this invention provides a nitrogen-polar c-plane surface of a GaN layer supported by a metallic plate. The coefficient of thermal expansion of the metallic plate matches that of GaN layer. The GaN layer is bonded to the metallic plate with bonding metal. The bonding metal not only bonds the GaN layer to the metallic plate but also covers the entire surface of the metallic plate to prevent corrosion of the metallic plate and optionally spontaneous nucleation of GaN on the metallic plate during the bulk GaN growth in supercritical ammonia. The bonding metal is compatible with the corrosive environment of ammonothermal growth.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to the following U.S. patent applications:

PCT Utility Patent Application Serial No. US2005/024239, filed on Jul.8, 2005, by Kenji Fujito, Tadao Hashimoto and Shuji Nakamura, entitled“METHOD FOR GROWING GROUP III-NITRIDE CRYSTALS IN SUPERCRITICAL AMMONIAUSING AN AUTOCLAVE,” attorneys' docket number 30794.0129-WO-01(2005-339-1);

U.S. Utility patent application Ser. No. 11/784,339, filed on Apr. 6,2007, by Tadao Hashimoto, Makoto Saito, and Shuji Nakamura, entitled“METHOD FOR GROWING LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS INSUPERCRITICAL AMMONIA AND LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS,”attorneys docket number 30794.179-US-U1 (2006-204), which applicationclaims the benefit under 35 U.S.C. Section 119(e) of U.S. ProvisionalPatent Application Ser. No. 60/790,310, filed on Apr. 7, 2006, by TadaoHashimoto, Makoto Saito, and Shuji Nakamura, entitled “A METHOD FORGROWING LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS IN SUPERCRITICALAMMONIA AND LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS,” attorneysdocket number 30794.179-US-P1 (2006-204);

U.S. Utility Patent Application Ser. No. 60/973,662, filed on Sep. 19,2007, by Tadao Hashimoto and Shuji Nakamura, entitled “GALLIUM NITRIDEBULK CRYSTALS AND THEIR GROWTH METHOD,” attorneys docket number30794.244-US-P1 (2007-809-1) and issued as U.S. Pat. No. 8,253,221 and9.243,344;

U.S. Utility patent application Ser. No. 11/977,661, filed on Oct. 25,2007, by Tadao Hashimoto, entitled “METHOD FOR GROWING GROUP III-NITRIDECRYSTALS IN A MIXTURE OF SUPERCRITICAL AMMONIA AND NITROGEN, AND GROUPIII-NITRIDE CRYSTALS GROWN THEREBY,” attorneys docket number30794.253-US-U1 (2007-774-2) and issued as U.S. Pat. No. 7,803,344;

Allowed U.S. Utility patent application Ser. No. 12/392,960, filed onFeb. 25, 2008, by Tadao Hashimoto, Edward Letts, Masanori Ikari,entitled “METHOD FOR PRODUCING GROUP III-NITRIDE WAFERS AND GROUPIII-NITRIDE WAFERS,” attorneys docket number 62158-30002.00 orSIXPOI-003;

U.S. Patent Application Ser. No. 61/058,900, filed on Jun. 4, 2008, byEdward Letts, Tadao Hashimoto, Masanori Ikari, entitled “METHODS FORPRODUCING IMPROVED CRYSTALLINITY GROUP III-NITRIDE CRYSTALS FROM INITIALGROUP III-NITRIDE SEED BY AMMONOTHERMAL GROWTH,” attorneys docket number62158-30004.00 or SIXPOI-002 and issued as U.S. Pat. No. 8,728,234;

U.S. Utility Patent Application Ser. No. 61/058,910, filed on Jun. 4,2008, by Tadao Hashimoto, Edward Letts, Masanori Ikari, entitled“HIGH-PRESSURE VESSEL FOR GROWING GROUP III NITRIDE CRYSTALS AND METHODOF GROWING GROUP III NITRIDE CRYSTALS USING HIGH-PRESSURE VESSEL ANDGROUP III NITRIDE CRYSTAL,” attorneys docket number 62158-30005.00 orSIXPOI-005 and issued as U.S. Pat. No. 8,236,237;

U.S. Utility Patent Application Ser. No. 61/131,917, filed on Jun. 12,2008, by Tadao Hashimoto, Masanori Ikari, Edward Letts, entitled “METHODFOR TESTING III-NITRIDE WAFERS AND III-NITRIDE WAFERS WITH TEST DATA,”attorneys docket number 62158-30006.00 or SIXPOI-001 and issued as U.S.Pat. Nos. 8,357,243, 8,585,822, and 8,557,043;

U.S. Utility patent application Ser. No. 12/580,849, filed on Oct. 16,2009, by Tadao Hashimoto, Masanori Ikari, Edward Letts, entitled“REACTOR DESIGN FOR GROWING GROUP III NITRIDE CRYSTALS AND METHOD OFGROWING GROUP III NITRIDE CRYSTALS,” attorneys docket number SIXPOI-004;

U.S. Utility Patent Application Ser. No. 61/694,119, filed on Aug. 28,2012, by Tadao Hashimoto, Edward Letts, Sierra Hoff, entitled “GROUP IIINITRIDE WAFER AND PRODUCTION METHOD,” attorneys docket number SIXPOI-015and issued as U.S. Pat. Nos. 9,543,393 and 8,921,231;

U.S. Utility Patent Application Ser. No. 61/705,540, filed on Sep. 25,2012, by Tadao Hashimoto, Edward Letts, Sierra Hoff, entitled “METHOD OFGROWING GROUP III NITRIDE CRYSTALS,” attorneys docket number SIXPOI-014and issued as U.S. Pat. Nos. 9,518,340 and 9,202,872;

Allowed U.S. Utility patent application Ser. No. 14/720,819, filed onMay 24, 2015, by Tadao Hashimoto, Edward Letts, entitles “GROUP IIINITRIDE BULK CRYSTALS AND THEIR FABRICATION METHOD,” attorneys docketnumber SIXPOI-020.

U.S. Utility patent application Ser. No. 15/004,464, filed on Jan. 22,2016, by Tadao Hashimoto, Edward Letts, Daryl key, entitles “SEEDSELECTION AND GROWTH METHODS FOR REDUCED-CRACK GROUP III NITRIDE BULKCRYSTALS,” attorneys docket number SIXPOI-024.

which are all incorporated by reference herein in their entirety as ifput forth in full below.

BACKGROUND Field of the Invention

The invention relates to seed crystals used for growth of galliumnitride (GaN) bulk crystals and their fabrication method. Bulk crystalsof GaN are sliced into semiconductor wafers to produce various devicesincluding optoelectronic devices such as light emitting diodes (LEDs)and laser diodes (LDs), and electronic devices such as transistors. Morespecifically, the invention provides large-area seed crystals forgrowing large-diameter bulk crystal of GaN in supercritical ammonia. Theinvention also provides the methods of making these seed crystals.

Description of the Existing Technology

This document refers to several publications and patents as indicatedwith numbers within brackets, e.g., [x]. Following is a list of thesepublications and patents:

-   [1] R. Dwiliński, R. Doradziński, J. Garczyński, L.    Sierzputowski, Y. Kanbara, U.S. Pat. No. 6,656,615.-   [2] R. Dwiliński, R. Doradziński, J. Garczyński, L.    Sierzputowski, Y. Kanbara, U.S. Pat. No. 7,132,730.-   [3] R. Dwiliński, R. Doradziński, J. Garczyński, L.    Sierzputowski, Y. Kanbara, U.S. Pat. No. 7,160,388.-   [4] K. Fujito, T. Hashimoto, S. Nakamura, International Patent    Application No. PCT/US2005/024239, WO07008198.-   [5] T. Hashimoto, M. Saito, S. Nakamura, International Patent    Application No. PCT/US2007/008743, WO07117689. See also    US20070234946, U.S. application Ser. No. 11/784,339 filed Apr. 6,    2007.-   [6] D′ Evelyn, U.S. Pat. No. 7,078,731.

Each of the references listed in this document is incorporated byreference in its entirety as if put forth in full herein, andparticularly with respect to their description of methods of making andusing group III nitride substrates.

GaN and its related group III nitride alloys are the key material forvarious optoelectronic and electronic devices such as LEDs, LDs,microwave power transistors, and solar-blind photo detectors. CurrentlyLEDs are widely used in displays, indicators, general illuminations, andLDs are used in data storage disk drives. However, the majority of thesedevices are grown epitaxially on heterogeneous substrates, such assapphire and silicon carbide because GaN substrates are extremelyexpensive compared to these heteroepitaxial substrates. Theheteroepitaxial growth of group III nitride causes highly defected oreven cracked films, which hinder the realization of high-end optical andelectronic devices, such as high-brightness LEDs for general lighting orhigh-power microwave transistors.

To solve the fundamental problems caused by heteroepitaxy, it isindispensable to utilize GaN wafers sliced from bulk GaN crystals. Forthe majority of devices, GaN wafers are favorable because it isrelatively easy to control the conductivity of the wafer and GaN waferwill provide the smallest lattice/thermal mismatch with device layers.However, due to the high melting point and high nitrogen vapor pressureat elevated temperature, it has been difficult to grow GaN crystalingots and slice them into wafers. Currently, the GaN wafers availablein market are mainly free-standing GaN wafers produced by a methodcalled hydride vapor phase epitaxy (HVPE). State of the art HVPEfree-standing GaN wafers are produced by growing a thick GaN layer on aheteroepitaxial substrate such as sapphire and gallium arsenide, whichis subsequently removed to make the layer free-standing. Due to this“quasi-bulk” method, it is difficult to reduce dislocation density lessthan 10⁵ cm⁻². Typically, HVPE-produced GaN has a dislocation densitybetween 1×10⁵ cm⁻² and 1×10⁸ cm⁻², whereas MOCVD and MBE-produced GaNhave a typical dislocation density between 1×10⁸ cm⁻² and 1×10⁹ cm⁻² andsodium flux-produced GaN has a dislocation density on the order of 1×10⁴cm⁻².

To obtain high-quality GaN wafers for which dislocation density is lessthan 10⁵ cm⁻², various growth methods such as ammonothermal growth, fluxgrowth, high-temperature solution growth have been developed.Ammonothermal method grows GaN bulk crystals in supercritical ammonia[1-6]. The flux method and the high-temperature solution growth use amelt of group III metal.

Recently, high-quality GaN substrates having dislocation density lessthan 10⁵ cm⁻² can be obtained by the ammonothermal growth. Since theammonothermal method can produce a true bulk crystal, one can grow oneor more bulk crystals and slice them to produce GaN wafers. In theammonothermal growth, bulk crystals of GaN are grown on seed crystals.However, since GaN crystals do not exist in nature, one must fabricate aGaN seed crystal with other method.

It is difficult to produce a seed crystal that is suitable for use inammonothermal bulk growth. Currently, ammonothermal growth of bulk GaNuses a free-standing HVPE GaN wafer. The highest quality free-standingHVPE GaN is selected through detailed analysis (US 2016-0215410) andbulk GaN crystal as large as 2″ in diameter can be obtained. However,due to large mismatch of the crystal lattice and thermal expansioncoefficient, it is extremely difficult to produce free-standing GaNwafers larger than 2 inch by HVPE. Although some producers havedemonstrated 4 inch and 6 inch GaN wafers by HVPE, the crystal qualityis not as good as 2 inch GaN wafers formed by HVPE due to the problemsassociated with the heteroepitaxy (e.g. cracks, breakage). The thermalexpansion mismatch causes large lattice curvature, which manifests assmall radius of curvature of the crystal lattice. In addition, thestress associated with the heteroepitaxy increase the chance of crackingduring processing, which decreases the production yield significantlyfor larger wafers. Currently, these technical limitations of HVPE limitthe available size of HVPE-produced seed for the ammonothermal bulkgrowth.

This invention discloses large-area seed crystals for growing bulkcrystal of GaN by the ammonothermal method. In addition, this inventiondiscloses methods of fabricating such seed crystals.

SUMMARY OF THE INVENTION

In one instance, the seed crystal of this invention comprises anitrogen-polar c-plane surface of a GaN layer supported by a metallicplate. The coefficient of thermal expansion of the metallic platematches that of the GaN layer, as discussed below. The GaN layer isbonded to the metallic plate with a corrosion-resistant adhesive such asa bonding metal. The adhesive not only bonds the GaN layer to themetallic plate but also covers the entire surface of the metallic platein order to prevent corrosion of the metallic plate and optionallyspontaneous nucleation of GaN on the metallic plate during bulk GaNgrowth in supercritical ammonia. The adhesive is compatible with thecorrosive environment of the ammonothermal growth.

The invention in one instance also provides a method of fabricating theseed crystal for growth of a GaN bulk crystal in supercritical ammonia.A high-quality GaN layer is grown on a heteroepitaxial substrate such assapphire. The surface of the GaN layer is gallium-polar c-plane. Then,the surface of the GaN layer is coated with the adhesive (e.g. bondingmetal). A metallic plate is prepared by coating the bonding metal on theentire surface of the metallic plate. The Ga-polar c plane of the GaNlayer is bonded against the metallic plate by melting the bonding metal.Then, the heteroepitaxial substrate is removed to expose the GaN layer'snitrogen-polar surface, and is optionally followed by polishing thenitrogen-polar surface.

In addition, the invention provides methods of growing bulk crystal ofgallium nitride using the seed crystal explained above in supercriticalammonia.

BRIEF DESCRIPTION OF THE DRAWINGS

Referring now to the drawings in which like reference numbers representcorresponding parts throughout:

FIG. 1 is a schematic drawing of the seed crystal

In the figure each number represents the followings:

1. A metallic plate,

2. Bonding metal,

3. GaN crystal layer,

3B. Nitrogen-polar c-plane surface of the GaN crystal layer.

FIG. 2 is a schematic drawing of the fabrication process of the seedcrystal depicted at steps A-G during fabrication of the seed crystal.

In the figure each number represents the followings:

1. A metallic plate,

2. Bonding metal,

3. GaN crystal layer,

3A. Gallium-polar c-plane surface of the GaN crystal layer,

3B. Nitrogen-polar c-plane surface of the GaN crystal layer,

4. A heteroepitaxial substrate,

5. Bonding metal on top of the gallium-polar c-plane surface of the GaNcrystal layer,

DETAILED DESCRIPTION OF THE INVENTION Technical Description of theInvention

The seed crystal of the present invention is used to grow bulk crystalof GaN in supercritical ammonia. The crystal growth method usingsupercritical ammonia is called ammonothermal growth. Through ourdevelopment of ammonothermal growth of bulk GaN crystals, we havediscovered several key technologies to obtain a crack-free GaN bulkcrystal up to 2 inches using a free-standing HVPE GaN wafer as a seedcrystal (e.g. Ser. Nos. 14/720,819, 15/004,464 above).

However, the market demands 4 inch or even larger GaN wafers produced bythe ammonothermal growth. Since the ammonothermal growth of GaNpractically does not allow lateral expansion of the crystal size duringgrowth, a 4 inch seed is needed to grow a 4 inch bulk crystal.

Unfortunately, a 4 inch free-standing HVPE GaN wafer having a sufficientstructural quality for the use of a seed crystal is not available atthis moment. The current limitation of the free-standing HVPE GaN is theaccumulated stress in the thick film on heteroepitaxial substrates suchas sapphire or gallium arsenide. To fabricate a free-standing GaN waferby removing the heteroepitaxial substrates, the HVPE-grown GaN filmthickness must exceed the final wafer thickness, i.e. 350 microns sothat the newly-grown GaN has sufficient strength to withstand variousforces during substrate separation and handling. In reality, due tomicrocracks in the film, the GaN layer must exceed at least 500 microns.Due to high residual stress of this structure, the production yield offree-standing HVPE GaN that is usable as a seed for ammonothermal growthis quite low.

In addition, when the wafer size becomes larger, the stress valueincreases by the power of two (i.e. stress is proportional to (length ordiameter)); therefore, it becomes extremely difficult to producefree-standing GaN wafers larger than 2 inches (surface area larger than20 cm) with maintaining their structural quality. This limitationimpedes the further development of GaN wafers by the ammonothermalgrowth. Therefore, this current invention presents an alternativestructure to provide a seed crystal for the ammonothermal bulk growth ofGaN.

FIG. 1 presents the schematic cross section of the seed crystal. Thenitrogen-polar c-plane surface, 3B, of the GaN crystal layer, 3, acts asseed. Since the thickness of the GaN crystal layer, 3, is not thickenough to sustain itself as free-standing, the layer is supported by ametallic plate, 1. The GaN crystal layer, 3, is bonded withcorrosion-resistant adhesive (here, bonding metal, 2), on the metallicplate, 1.

To avoid cracking of the GaN crystal layer, 3, during bonding andammonothermal growth, the coefficient of thermal expansion of themetallic plate, 1, is closely matched to the GaN crystal layer, 3,preferably within ±20% of the coefficient of thermal expansion of GaN.Since the coefficient of thermal expansion of GaN is about 5.6e-6 (/K),tungsten, molybdenum, and hafnium can be used for the metallic plate.The coefficient of thermal expansion of tungsten, molybdenum, andhafnium is 4.5e-6 (/K), 5.0e-6 (K), and 5.9e-6 (/K), respectively. Inaddition, by forming an alloy based on these metals, the coefficient ofthermal expansion can be matched closer. For example, by adding copperand nickel in tungsten, the coefficient of thermal expansion can beadjusted to 5.4e-6 (/K) or even closer to that of GaN. The metallicplate is sufficiently rigid that the thin GaN layer adhered to itssurface is strong and withstands mechanical handling as well as stressesencountered during temperature changes encountered in the ammonothermalreactor. For example, a metallic plate may be between 0.2 mm and 5 mmthick.

In addition to the coefficient of thermal expansion, thermalconductivity can also be an important factor for avoiding cracks duringbonding and ammonothermal growth in commercial processes. The thermalconductivity of tungsten, molybdenum and hafnium is 174 (W/m K), 138(W/m K), and 23 (W/m K), respectively. Thus, tungsten, molybdenum andtheir alloys can serve as a good heat distributor during bonding andcrystal growth. Especially, temperature non-uniformity during themelting and cooling process of the bonding metal causes cracking of theGaN crystal film. Therefore, it is preferable to choose a metal havingthermal conductivity larger than 100 W/m K.

The corrosion-resistant adhesive (e.g. bonding metal) can serve threemajor roles if desired. The first role is that the adhesive bonds theGaN crystal layer to the metallic plate. To reduce the thermal stressand shock, it is preferable to use a bonding metal with lower meltingpoint than the metallic plate's melting point. Second, the adhesiveprotects the metallic plate from the corrosive environment ofammonothermal growth. Since supercritical ammonia used in theammonothermal growth is highly corrosive, the metallic plate is easilyetched. By coating the entire surface of the metallic plate with anadhesive such as a bonding metal, such corrosion can be avoided. Thirdand optionally, the adhesive can help to prevent spontaneous nucleationof GaN during ammonothermal growth, thereby reducing parasiticdeposition of GaN on the plate. Silver, for example, meets all threeconditions, although other metals such as gallium, indium, eutectic goldtin or other eutectic bonding metal can be used.

Bulk growth of GaN in supercritical ammonia requires nitrogen-polarc-plane surface of GaN. The seed crystal of the present inventionprimarily exposes the nitrogen-polar c-plane surface of GaN. Thegallium-polar c-plane surface of GaN is attached to the metallic plateand not exposed.

By growing the GaN crystal layer to the minimum thickness needed toreliably separate a thin HVPE-produced GaN layer from its substrate, thelattice curvature caused by accumulated stress can be reduced. So, it ispossible to have HVPE-produced GaN crystal layer with curvature radiuslarger than 5 m. Larger curvature radius is beneficial to reduction ofcracks in the bulk crystal. To achieve this situation, the thickness ofthe GaN crystal layer is controlled between 10 and 150 microns.

FIG. 2 presents the process flow to produce the seed crystal in thepresent invention. FIG. 2 A shows a heteroepitaxial substrate, 4. Amongthe potential heteroepitaxial substrates such as sapphire, siliconcarbide, silicon, and gallium arsenide, sapphire yields the GaN crystallayer with the highest structural quality. So, it is preferable to usesapphire. The surface orientation is c-plane.

To grow GaN crystal layer on sapphire, vapor phase method such as HVPE,metalorganic chemical vapor deposition (MOCVD), molecular beam epitaxy,and sputtering, pulsed laser deposition can be used. Currently HVPE isthe most preferred method to obtain GaN crystal layer of thicknessbetween 10 and 150 microns. Also, liquid phase method such as sodiumflux method can be used as well. By minimizing the layer thickness, theamount of stress in the GaN crystal layer can be minimized. This willminimize the lattice curvature and cracking. The cross-section of theGaN crystal layer, 3, grown on a heteroepitaxial substrate, 4, is shownin FIG. 2B. The top surface of the GaN crystal layer is gallium polarc-plane, 3A.

After the growth of the GaN crystal layer, 3, on the heteroepitaxialsubstrate, 4, bonding metal, 5, is deposited on the top surface of theGaN crystal layer, 3, as shown in FIG. 2C. Silver is the most preferablematerial for the bonding metal although other metals including gallium,indium, eutectic gold tin or other eutectic bonding metal can be used. Aconventional metallization process such as thermal evaporation, e-beamevaporation and sputtering can be used. If necessary, another metal canbe inserted between the GaN crystal layer and the bonding metal toensure adhesion of the bonding metal to the GaN crystal layer. Forexample, to ensure adhesion of silver adhesive to the Ga polar surfaceof the GaN crystal layer, nickel can be inserted between silver and theGaN crystal layer. Nickel can be deposited using a conventional methodsuch as electron beam evaporation.

A metallic plate, 1, is prepared (FIG. 2D) to support the GaN crystallayer. The entire surface of the metallic plate is preferably coatedwith the bonding metal as shown in FIG. 2E (optionally including theplate's edges as well as the plate's major surfaces). This can be donewith electroplating or other coating method.

Then, the GaN crystal layer on the heteroepitaxial substrate is pressedagainst the metallic plate (FIG. 2F) The parts are heated whilemaintaining pressure on the parts to melt the bonding metal and assurethat the parts maintain contact with the bonding metal acting as thecorrosion-resistant adhesive. After melting the bonding metal, the partis cooled to room temperature. The temperature ramp rate and coolingrate are sufficiently low to avoid cracking the thin GaN crystal layer,3.

After bonding, the heteroepitaxial substrate, 4, is removed (FIG. 2G).When a double-side polished sapphire substrate is used to form the thinGaN layer via e.g. hydride vapor phase epitaxy, the sapphire substratecan be removed by irradiating the backside of the sapphire usingultraviolet laser light (laser lift-off). The laser light is absorbed atthe interface between the GaN crystal layer and the sapphire anddecomposes GaN, leaving metallic gallium at the interface. By heatingthe part to a temperature higher than the melting point of gallium, thesapphire substrate can be removed from the thin GaN layer. Another wayof removing the heteroepitaxial substrate is to mechanically grind thesubstrate. Using diamond grinding wheel, the heteroepitaxial substratecan be removed.

The general method described above may also be modified as follows. TheGaN crystal layer and substrate may be irradiated using UV laser lightto partially damage their interface and provide a very small amount ofmetallic gallium between GaN and substrate at the interface. Laserirradiation can occur either before bonding metal is applied or afterbonding metal is applied to the Ga-polar surface of the GaN layer andbefore bonding the GaN layer to the metal plate. This method enables thesubstrate (e.g. sapphire) to separate from the GaN layer more easily oreven self-separate during cooling after the metal plate has been bondedto the GaN layer and its substrate. Consequently, it may not benecessary to irradiate the GaN-substrate interface after bonding the GaNlayer and its substrate to the metal plate, although this step may beperformed if desired.

After removal of the heteroepitaxial substrate, the exposed nitrogenpolar c-plane of GaN crystal layer is lapped, mechanically polished andchemomechanically polished to obtain an appropriate surface quality forgrowth of bulk GaN by the ammonothermal method. The removal ofsubsurface damage can be evaluated by a glancing angle x-ray rockingcurve using 114 diffraction plane of GaN (U.S. Ser. No. 13/798,580).

Example 1

A GaN crystal layer having thickness of 20 microns is grown on adouble-side polished 4″ c-plane sapphire substrate. The dislocationdensity of the GaN crystal layer is in the order of 10⁷ cm⁻², confirmedwith cathodeluminescence. The top surface of the GaN crystal layer isgallium polar c-plane. Using electron beam evaporator, silver isdeposited on the gallium polar c-plane surface of the GaN crystal layer.The thickness of the silver is approximately 0.5 micron, measured withthickness monitor of the electron beam evaporator. A 4″ metallic platemade of tungsten-nickel-copper alloy (90% W 6% Ni 4% Cu) is prepared.The coefficient of thermal expansion is about 5.4e-6 (1/K) and thermalconductivity is about 230 W/m K. The thickness of the plate is ⅛″. Theentire surface of the metallic plate is electroplated with silver. TheGaN crystal layer on the 4″ sapphire is placed on top of the metallicplate so that the silver layers of the both parts meet together. Aweight plate made of the tungsten alloy is placed on top of the sapphireto apply compressive pressure to the parts. The three pieces of theplates (i.e. the silver plated metallic plate, GaN crystal layer onsapphire and the weight plate) are loaded into an electric furnace. Thefurnace temperature is raised to 1000° C. in 1 hour, held for 10 minutesand cooled to 900° C. in 15 minutes. The furnace was maintained at 900°C. for 30 minutes and then cooled to the room temperature in 2 hours.Holding the temperature at 900° C. ensures complete bonding of the GaNcrystal layer to the metallic plate with maintaining the flatness of theGaN crystal layer. This is explained as follows: The as grown GaNcrystal layer on sapphire is typically bowed convex toward the galliumpolar c-plane at room temperature due to mismatch of the coefficient ofthermal expansion between GaN and sapphire. This bi-layer structureflattens at 1000° C. because the GaN crystal layer is typically grown atabout 1000° C. Therefore, the GaN crystal layer on sapphire flattens at1000° C., at which temperature silver melts. Holding the temperature at900° C. helps the GaN crystal layer bonds to the metallic place flat.After the complete bonding, the metallic plate prevents bowing of thesapphire upon cooling. This way, the GaN crystal layer is attached flatto the metallic plate. If heating and cooling is too fast, the GaNcrystal layer as well as the sapphire can be cracked. The high thermalconductivity of the W—Ni—Cu alloy helps to equalize the temperature overthe entire area. After cooling the attached parts, excimer laser lightis irradiated to the backside for the sapphire. Since the laser spot isabout 3 mm×3 mm, scanning of the work piece is required to irradiate theentire backside of the part. After irradiation of UV laser light, thepart is heated to 40° C. in water to remove the sapphire (laser lift-offprocess). The exposed nitrogen polar surface of the GaN crystal layer islapped with 3 micron diamond slurry, polished with 1 micron diamondslurry and chemomechanically polished with CMP slurry. This way, theseed crystal of the present invention is produced. Other seeds areproduced by substituting the following metallic plates individually inplace of the tungsten-nickel-copper alloy: tungsten (pure); molybdenum;Mo-0.5Ti-0.08Zr (TZM) alloy; hafnium; Hf-(0.6-2.1)Zr.

Other seeds are produced using gallium, indium, and eutectic gold tinbonding metals individually in place of silver in each of the platesabove.

Gallium nitride thin films are formed by depositing them on AlN andAlGaN transition layers deposited on silicon substrates. Other thingallium nitride films are formed on a silicon carbide substrate as well.

Other seeds of the invention are produced by repeating the procedureabove on the opposite side of the metal plate, so that the metallicplate has a first gallium nitride layer on a first side of the metallicplate and a second gallium nitride layer on the second side of themetallic plate. The exposed gallium nitride surfaces may both benitrogen-polar surfaces, for instance.

Example 2

A GaN crystal layer having thickness of 20 microns is grown on adouble-side polished 4″ c-plane sapphire substrate. The dislocationdensity of the GaN crystal layer is in the order of 10⁷ cm⁻², confirmedwith cathodeluminescence. The top surface of the GaN crystal layer isgallium polar c-plane. The interface between the GaN crystal layer andthe sapphire substrate is irradiated with UV laser from backside inorder to partially damage the interface. This process inducesself-separation of the sapphire substrate during cooling after bonding.Using electron beam evaporator, silver is deposited on the gallium polarc-plane surface of the GaN crystal layer. The thickness of the silver isapproximately 0.5 micron, measured with thickness monitor of theelectron beam evaporator. A 4″ metallic plate made oftungsten-nickel-copper alloy (90% W 6% Ni 4% Cu) is prepared. Thecoefficient of thermal expansion is about 5.4e-6 (1/K) and thermalconductivity is about 230 W/m K. The thickness of the plate is ⅛″. Theentire surface of the metallic plate is electroplated with silver. TheGaN crystal layer on the 4″ sapphire is placed on top of the metallicplate so that the silver layers of the both parts meet together. Aweight plate made of the tungsten alloy is placed on top of the sapphireto apply compressive pressure to the parts. The three pieces of theplates (i.e. the silver plated metallic plate, GaN crystal layer onsapphire and the weight plate) are loaded into an electric furnace. Thefurnace temperature is raised to 1000° C. in 1 hour, held for 10 minutesand cooled to 900° C. in 15 minutes. The furnace was maintained at 900°C. for 30 minutes and then cooled to the room temperature in 2 hours.Holding the temperature at 900° C. ensures complete bonding of the GaNcrystal layer to the metallic plate with maintaining the flatness of theGaN crystal layer. During cooling, the thermal shrink of sapphire causeshorizontal breakage along the pre-induced damage between the GaN crystallayer and sapphire, resulting in self-separation of sapphire from thepart. The high thermal conductivity of the W—Ni—Cu alloy helps toequalize the temperature over the entire area. The exposed nitrogenpolar surface of the GaN crystal layer is lapped with 3 micron diamondslurry, polished with 1 micron diamond slurry and chemomechanicallypolished with CMP slurry. This way, the seed crystal of the presentinvention is produced.

Example 3

Any of the seeds as formed in Example 1 or Example 2 are placed in anautoclave along with ammonia, nutrient such as recycled gallium nitrideand/or gallium, and a mineralizer (acidic or basic such as metallicsodium). The autoclave is heated so that the chamber within theautoclave attains sufficient temperature and pressure for the ammonia tobe supercritical and sufficient for ammonothermal gallium nitridegrowth. The autoclave is maintained under ammonothermal growthconditions for a sufficient time to form a bulk crystal of galliumnitride using the gallium nitride layer adhered to the metallic plate.The metallic plate is separated from the bulk crystal by e.g. heatingthe bulk crystal and metallic plate to a temperature that releases themetallic plate from the bulk crystal. For instance, the temperature isincreased above the melt point of a bonding metal used to adhere to themetallic plate. Alternatively, the metallic place is separated from thebulk crystal by cutting the crystal with a mechanical way such as a wiresaw or inner-blade cutter.

Thus, the invention in various embodiments includes:

-   -   1. A seed crystal for growing a gallium nitride bulk crystal in        supercritical ammonia comprising a metallic plate and a gallium        nitride crystal layer adhered to the metallic plate with a        corrosion resistant adhesive, wherein        -   (a) the gallium-polar c-plane of the gallium nitride crystal            layer is bonded to the metallic plate by the corrosion            resistant adhesive and the corrosion resistant adhesive            comprises a bonding metal,        -   (b) the nitrogen-polar c-plane of the gallium nitride            crystal layer has a surface area preferably larger than 20            cm², and        -   (c) the difference between the thermal expansion coefficient            of the gallium nitride crystal layer and the metallic plate            is less than 20% of the thermal expansion coefficient of the            gallium nitride crystal layer.    -   2. A seed crystal according to paragraph 1, wherein the thermal        conductivity of the metallic plate is larger than 100 W/m K.    -   3. A seed crystal according to paragraph 1 or paragraph 2,        wherein the metallic plate comprises tungsten or tungsten alloy.    -   4. A seed crystal according to any of paragraphs 1 through 3,        wherein the bonding metal is composed of a different kind of        metal from the metallic plate, and the melting temperature of        the bonding metal is lower than the metallic plate.    -   5. A seed crystal according to any paragraphs 1 through 4,        wherein the bonding metal covers the entire surface of the        metallic plate so that the only exposed materials of the seed        crystal are the gallium nitride crystal and the bonding metal.    -   6. A seed crystal according to paragraph 5, wherein the bonding        metal has insufficient reactivity with gallium and with nitrogen        under ammonothermal growth conditions to prevent spontaneous        nucleation of gallium nitride crystal in supercritical ammonia.    -   7. A seed crystal according to paragraph 6, wherein the bonding        metal comprises silver.    -   8. A seed crystal according to any of paragraphs 1 through 7,        wherein the thickness of the gallium nitride crystal layer is        more than 10 microns and less than 150 microns.    -   9. A seed crystal according to any of paragraphs 1 through 8,        wherein the lattice curvature of the gallium nitride crystal        layer is more than 5 m.    -   10. A seed crystal according to paragraph 9, wherein the surface        of the nitrogen polar c-plane of the gallium nitride crystal is        a polished surface with sufficient smoothness to provide a        suitable surface for bulk crystal growth in supercritical        ammonia.    -   11. A seed crystal according to any of paragraphs 1 through 10,        wherein the gallium nitride crystal has a dislocation density        greater than 10⁵ cm⁻².    -   12. A seed crystal according to paragraph 11, wherein the        gallium nitride crystal has a dislocation density between 1×10⁵        cm⁻² and 1×10⁷ cm⁻².    -   13. A seed crystal according to any of paragraphs 1 through 12,        wherein the gallium nitride crystal is a hydride vapor phase        epitaxy crystal.    -   14. A seed crystal according to any paragraph above wherein the        nitrogen polar surface of the gallium nitride crystal is exposed        for bulk crystal growth.    -   15. A seed crystal according to any of paragraphs 1 through 13,        wherein the seed crystal further comprises a substrate in        contact with the nitrogen polar surface of the gallium nitride        crystal, and metallic gallium is present at the interface        between the substrate and the nitrogen polar surface.    -   16. A method of fabricating a seed crystal for growing a gallium        nitride bulk crystal in supercritical ammonia comprising:        -   (a) coating the gallium polar c-plane surface of a gallium            nitride crystal layer with a corrosion resistant adhesive            that comprises a bonding metal,        -   (b) coating the entire surface of a metallic plate with the            corrosion resistant adhesive,        -   (c) bonding the gallium polar c-plane to the metallic plate            with the bonding metal, and        -   (d) removing the substrate to expose the nitrogen polar            c-plane of the gallium nitride crystal layer.    -   17. A method of fabricating a seed crystal according to        paragraph 16, wherein the difference of the thermal expansion        coefficient between the gallium nitride crystal layer and the        metallic plate is less than 20% of the thermal expansion        coefficient of the gallium nitride crystal layer, and the        thermal conductivity of the metallic plate is larger than 100        W/m K.    -   18. A method of fabricating a seed crystal according to        paragraph 16 or paragraph 17, wherein the metallic plate        comprises tungsten or tungsten alloy.    -   19. A method of fabricating a seed crystal according to any of        paragraphs 16 through 18, wherein the corrosion resistant        adhesive comprises a bonding metal composed of a different kind        of metal from the metallic plate, and the melting temperature of        the bonding metal is lower than the metallic plate.    -   20. A method according to paragraph 19 comprising melting the        bonding metal to secure the gallium nitride layer to the        metallic plate.    -   21. A method of fabricating a seed crystal according to        paragraph 19 or paragraph 20, wherein the bonding metal has a        sufficient low reactivity with gallium and with nitrogen under        ammonothermal growth conditions to prevent spontaneous        nucleation of gallium nitride in supercritical ammonia.    -   22. A method of fabricating a seed crystal according to any of        paragraphs 16 through 21, wherein the bonding metal is silver.    -   23. A method of fabricating a seed crystal according to        paragraphs 19 through 22, wherein the substrate is c-plane        sapphire and the thickness of the crystalline gallium nitride        layer is less than 150 microns.    -   24. A method of fabricating a seed crystal according to        paragraph 23, wherein the step (d) utilizes laser irradiation of        the interface between the gallium nitride crystal layer and the        substrate.    -   25. A method according to paragraph 24, wherein the laser        irradiation occurs prior to step (c) of paragraph 16.    -   26. A method of fabricating a seed crystal according to        paragraph 23, wherein the step (d) utilizes mechanical grinding.    -   27. A method according to any of paragraphs 16 through 26        further comprising polishing the nitrogen polar c-plane of the        gallium nitride crystal layer.    -   28. A method of fabricating a seed crystal according to        paragraph 27, wherein the lattice curvature of the gallium        nitride crystal layer is more than 5 m.    -   29. A method of removing a GaN crystal layer from a substrate on        which the GaN crystal layer was grown and consequently has        crystalline structure continuity at the interface,        comprising (a) irradiating the interface with UV light to damage        the crystalline material and form metallic gallium at the        interface; (b) adhering the GaN crystal layer to a metal plate        using an adhesive, thereby forming a unitary structure; and (c)        cooling the unitary structure to release the substrate from the        GaN crystal layer that is adhered to the metal plate.    -   30. A method according to any of paragraphs 16 through 29,        wherein the gallium nitride crystal layer has a dislocation        density greater than 10⁵ cm⁻².    -   31. A method according to paragraph 30, wherein the gallium        nitride crystal layer has a dislocation density between 1×10⁵        cm⁻² and 1×10⁷ cm⁻².    -   32. A method according to any of paragraphs 16 through 31,        wherein the gallium nitride crystal layer is a hydride vapor        phase epitaxy crystal.    -   33. A method according to any of paragraphs 29 through 32,        wherein the metallic plate comprises tungsten or tungsten alloy.    -   34. A method according to any of paragraphs 29 through 33,        wherein the corrosion resistant adhesive comprises a bonding        metal.    -   35. A method according to paragraph 34 comprising melting the        bonding metal to secure the gallium nitride layer to the        metallic plate.    -   36. A method according to paragraph 34 or paragraph 35, wherein        the bonding metal has a sufficient low reactivity with gallium        and with nitrogen under ammonothermal growth conditions to        prevent spontaneous nucleation of gallium nitride in        supercritical ammonia.    -   37. A method according to any of paragraphs 34 through 36,        wherein the bonding metal is silver.    -   38. A method according to paragraphs 29 through 37, wherein the        substrate is c-plane sapphire and the thickness of the        crystalline gallium nitride layer is less than 150 microns.    -   39. A method of growing gallium nitride bulk crystal using the        seed crystal of any of paragraphs 1 through 15 in ammonothermal        growth of gallium nitride in supercritical ammonia.

Advantages and Improvements

The size of the GaN layer of the seed crystal of this invention istherefore not limited and can be e.g. 6 inch because currently 6 inchsapphire substrates can be obtained commercially. In addition, ifsilicon is used as a substrate, the GaN layer can be as large as 450 mmusing commercially-available Si wafers. The present invention obviouslyhas the advantage of providing very large seed crystals for use inammonothermal growth, where the seed crystals are formed by a methodother than the ammonothermal method. In addition, by using a relativelythin layer of GaN crystal (10˜150 microns vs. 350˜450 microns forfree-standing GaN), the cost to produce the seed crystal of thisinvention is greatly reduced. Further, due to reduced residual stress inthe thin GaN crystal layer, the invention can also reduce theprobability that the thin GaN layer cracks during ammonothermal growth,resulting in higher production yield for the seed crystal of theinvention.

Possible Modifications

Although the example describes a double-side polished sapphire as asubstrate, other substrates such as a single-side polished sapphire,silicon carbide, silicon, and gallium arsenide can be used as analternative substrate.

Although the example describes tungsten-nickel-copper alloy as amaterial for the metallic plate, other metallic plate such astungsten-nickel-iron alloy, other tungsten alloy, pure tungsten,molybdenum, and molybdenum alloys can be used as long as the differenceof the coefficient of thermal expansion from GaN is less than 20% andthermal conductivity is more than 100 W/m K.

Although the preferred embodiment describes HVPE as an epitaxial growthmethod, other methods such as MOCVD, MBE, a flux method, high-pressuresolution growth, sputtering or pulsed laser deposition can be used aslong as they are compatible with the substrates.

Although the preferred embodiment describes a seed crystal having adiameter of 4″, similar benefit of this invention is expected for alarger diameter such as 6″ and larger.

Although the preferred embodiment describes silver as a bondingmaterial, other bonding material such as gallium, indium, eutectic goldtin or other eutectic bonding metals can be used as long as the metal ischemically compatible with the ammonothermal growth environment andoptionally prevents spontaneous nucleation of GaN during theammonothermal growth.

Although the example describes a laser lift-off to remove the sapphiresubstrate, other methods such as mechanical grinding can be used toremove the substrate.

What is claimed is:
 1. A method of removing a GaN crystal layer from asubstrate on which the GaN crystal layer was grown and consequently hascrystalline structure continuity at the interface, comprising (a)irradiating the interface with UV light to damage the crystallinematerial and form metallic gallium at the interface; (b) adhering theGaN crystal layer to a metal plate using an adhesive, thereby forming aunitary structure; and (c) cooling the unitary structure to release thesubstrate from the GaN crystal layer that is adhered to the metal plate.2. A method according to claim 1, wherein the gallium nitride crystallayer has a dislocation density greater than 10⁵ cm⁻².
 3. A methodaccording to claim 2, wherein the gallium nitride crystal layer has adislocation density between 1×10⁵ cm⁻² and 1×10⁷ cm⁻².
 4. A methodaccording to claim 1, wherein the gallium nitride crystal layer is ahydride vapor phase epitaxy crystal.
 5. A method according to claim 1,wherein the metallic plate comprises tungsten or tungsten alloy.
 6. Amethod according to claim 1, wherein the corrosion resistant adhesivecomprises a bonding metal.
 7. A method according to claim 6 comprisingmelting the bonding metal to secure the gallium nitride layer to themetallic plate.
 8. A method according to claim 7, wherein the bondingmetal has a sufficient low reactivity with gallium and with nitrogenunder ammonothermal growth conditions to prevent spontaneous nucleationof gallium nitride in supercritical ammonia.
 9. A method according toclaim 8, wherein the bonding metal is silver.
 10. A method according toclaim 1, wherein the substrate is c-plane sapphire and the thickness ofthe crystalline gallium nitride layer is less than 150 microns.